Sample preparation is the main bottleneck of the analytical process, especially when trace analysis is the purpose. The high demand for sustainable and more environmentally benign procedures has driven the development of solventless microextraction techniques in environmental analysis. This dissertation presents the development of novel solid-phase microextraction (SPME) and liquid-phase microextraction (LPME) based microextraction techniques for the extraction and determination of trace organic pollutants in the environmental aqueous samples. In the SPME based technique, the polymeric Kevlar fiber was employed as a novel sorbent, with advantages of robustness, cost-effectiveness, good storage performance and portability. In the LPME based approach, two solvent microextraction techniques (agitation-assisted dispersive liquid-liquid microextraction and hollow fiber LPME) were successfully combined for sample pretreatment, which greatly reduced solvent consumption, expanded the solvent choices, and provided effective cleanup. In conclusion, both developed techniques proved to be rapid screening, easily accessible and simple applicability approaches for environmental analysis.